Process for treating hydrocarbon oils



A ril 17, 1934. G. EGLOFF PROCESS FOR TREATING HYDROCARB ON OILS Filed Oct. 31, 1950 W\ ZEDJOU HHHI HI I I UM O llllllll INVENTOR GUSTAV EGLOFF BY M02 Q ATTORNEY Patented Apr. 17, 1934 335%,.

PROCESS FOR TREATING HYDROCARBON OILS Gustav Eglofi, Chicago, Ill., assignor to Universal, Oil Products Company, Chicago, 111., a corporation of South Dakota Application October 31, 1930, Serial No. 492,399

2 Claims. (Cl. 196144) This invention relates to the treatment of hy- 3 and is fed therefrom through line 4, valve 5, drocarbon oils. 7 line 6 and valve 7 into heating element 8, which It further relates to processes for improving is located in any suitable form of furnace 9 and the character of hydrocarbons by subjecting them in which the oil is heated under any desired to photochemical influence. pressure conditions, preferably to a temperature 60 It is a feature of the invention to treat hydrosufiicient to effect subsequent vaporization of carbon oils in the presence of chemical agents substantially all of the distillate. which will improve the character of the oils, as A treating agent, such as, for example, a soluby decreasing the gum and sulfur content and tion of zinc chloride and water, supplied through 10 by increasing color stability. line 10 and valve 11 to pump 12, may be fed 65 More particularly, the invention pertains to a through valve 13 in line 6, combining therein process for effecting the simultaneous eliminawith the oil to be treated, and passing through tion of gum-forming components, gums and sulvalve 7 to heating element 8. fur containing compounds from light hydrocar- If the material supplied to heating element 8 bcn oils, and in its more specific aspect it comis a distillate, such as that ordinarily produced 70 prises the chemical treatment of oils in the presby the cracking of heavier oils, which comprises ence of light, preferably ultra-violet light, to a substantial proportion of material boiling witheffect this result. in the range of motor fuel and heavier compo- It is known to the art that gums and gumnents boiling above the range of motor fuel, the

forming components of light mineral oils, such treating process here described preferably also 75 as cracked distillates, may beacted upon in the embodies redistillation of the distillate to effect presence ofcertain agents such as zinc and copseparation of the motor fuel components from per chlorides, or other salts, to facilitate their the heavier components of the distillate. If, removal. Such treatment may produce acolorhowever, the oil to be treated corresponds substable oil. Ordinary treatment of oils with zinc stantially in boiling range to motor fuel, the

chloride or its equivalent, effects no substantial heating to which it is subjected in heating eledesulfurization, and subsequent treatment is necment 8, may be simply for the purpose of vaporizessary for diminishing the sulfur content. ing the oil or may be employed for the purpose In accordance with the practice of this invenofincreasing the activity of the treating agent tion, however, it has been found that light rays, introduced to the heating element together with $5 and particularly ultra-violet light, have a benethe oil as already described. ficial effect on the activity of metal salts, such Heated materials from heating element 8 are as zinc chloride, when utilized in the treatment discharged through line 14 and valve 15 into the of hydrocarbons, a substantial desulfurization lower portion of treating and fractionating coltaking place simultaneously with the removal of umn 16. Column 16 may be of any suitable the gum and gum-forming constituents. form of contacting or fractionating device, such In t Carrying Out Of e preferred form of as a packed or bubble tower or a column conthe process embodying the invention, ultra-violet taining perforated pans, or the like, through light will be used, but the character of light which the heated vapors rise and are intimately ray m y be varied from the short w v portion contacted with a treating agent, such as a soluof the Sp through the ible portion and tion of zinc chloride and water, which is supplied into the infra-red portion. The suns rays or through line 17 and valve 18, and fed by means artificial light closely approximating the characof pump 19 through line 20 and valve 21 to the ter of the suns rays may be e p y treating and fractionating column 16.

It will be understood that the invention is not Treating and fractionating column 16, aside no to be limited as to the character of the reagents from it function as a, treating olumn, in which used, or the Specific S p Outlined in he p ethe chemical reagent is contacted with the oil, ferred form of the process to be hereinafter demay serve as a, fractionating zone to effect sep- SCribed- The following description the paration of the lighter from the heavier com- 50 paratus as illustrated in the drawing, and of the ponents of the oil undergoing treatment. In

process employing the apparatus, is to be taken this case, the heavier components of the distilmerely as illustrative of the features of the inlate are condensed and returned to the lower porvention. .tion of column 16 and are withdrawn through Referring to the drawing, the oil to be treated line 22 and valve 23. 55 is supplied through line 1 and valve 2 to pump A substantial proportion, if not all, of the water content in the solution of the zinc chloride will be evaporated by contact with the hot vapors in column 16, and the spent zinc chloride, together with sludge from the treating reaction, may be withdrawn from the bottom of the column through line 24 and valve 25. A dispersion of zinc chloride in the heavier components of the oil, which are refluxed to the bottom of column 16, which dispersion may still have value as a treating solution, may be withdrawn from the column through line 26 and valve 2'? and recirculated by means of pump 28 through line 29 and valve 30 back into column 16, preferably at or near the mid-portion of the column.

A source of light, such as for example a mercury vapor bulb 31, is placed within the treating and fractionating column 16, and is supplid with electrical energy through lines 32. It will be understood that any suitable source of light other than a mercury bulb, such as, for example, a carbon are or any incandescent bulb, may be employed, and it will also be apparent that instead of locating the source of light within column 16, it may be located exterior to the column, and the light may be admitted to the interior of the column through suitable windows not shown in the drawing, in which case glass of suitable composition, well known to the art, capable of admitting the desired light rays, is employed. The source of light is in all cases so located that the light rays are directed upon the oil undergoing treatment with treating solution, and to insure effective distribution of the light rays a plurality of sources of light may be employed, if desired, in which case it will be understood that each source of light may emit substantially the same or different light rays, so that the oil undergoing treatment in various portions of the apparatus may be subjected to the same or to different light rays as desired.

The treated vapors from column 16 are withdrawn through line 33 and valve-34, and may be subjected to any further chemical treatment which may be desired, or may be subjected to condensation, cooling and collection, by well known means not illustrated in the drawing.-

The treating process embodied by the present invention may be accomplished under any desired temperature and pressure conditions. The temperatures employed may range from substantially atmospheric. temperatures to cracking temperatures of a high order, generally termed vapor phase cracking temperatures; and pressure employed may vary from sub-atmospheric to high super-atmospheric pressures as high as 2000 pounds or more per square inch. Preferably, however, in an apparatus, such as illustrated in the drawing, the temperatures em ployed are below the ordinary cracking range, being only sufficient to effect redistillation of the distillate. All the pressures employed are preferably substantially atmospheric or relative- 1y low super-atmosphericv pressures and may be substantially'equalized throughout the system or may be lower upon column 16 than upon heating element 8.

As a specific example of the operation of the process of the invention in an apparatus, such as illustrated, a cracked distillate of about 50 degrees A. P. I. gravity, containing some per cent of motor fuel, is subJected in the heating element to a temperature of approximately 600 degrees F. An percent solution of zinc chloride and water amountingto about 5 percent by weight of the oil undergoing treatment is also supplied to the heating element. A pressure of about 100 pounds per square inch is maintained in the heating element, this pressure being sufficient to maintain a substantial proportion of the oil in the liquid state in this zone, but permitting the formation of steam at a tempera.- ture employed from the water in the treating solution, thus effecting dispersion of the zinc chloride in the oil being heated.

The pressure in the treating and fractionating column is reduced to substantially atmospheric pressure, permitting vaporization in substantially all of the heated oil. A 40 percent solution of zinc chloride and water amounting to approximately 10 percent by weight of the oil treated is introduced into the treating and fractionating column, passing down through the column countercurrent to the ascending vapors and being intimately contacted with these vapors in the presence of ultra-violet light supplied substantially as described.

Treated gasoline vapors are removed from the top of the treating column and are condensed and collected, while pressure distillate bottoms are withdrawn from the lower portion of the fractionating column.

Aside from effecting separation of the gasoline light components of the distillate from its heavier components, and reducing the gum content to some 25 milligrams as compared with about 350 milligrams of gum in the untreated distillate, the sulfur content of the gasoline may be reduced to 0.2 percent or less, as compared with approximately 0.5 percent in the untreated distillate, and the gasoline may be rendered a stable water white color even after prolonged exposure to sunlight.

Having thus described my invention, what I claim is:

1. A process for improving the character of hydrocarbon oils comprising vaporizing a hydrocarbon oil, refluxing the vapors, treating the vapors by commingling a non-volatile treating agent capable of decreasing the gum content and of eifecting a color stabilization of the oil, re-

circulating treating agent in the reflux con- 

